WO2014128421A1 - Substrate for device having an organic light-emitting diode - Google Patents

Substrate for device having an organic light-emitting diode Download PDF

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Publication number
WO2014128421A1
WO2014128421A1 PCT/FR2014/050370 FR2014050370W WO2014128421A1 WO 2014128421 A1 WO2014128421 A1 WO 2014128421A1 FR 2014050370 W FR2014050370 W FR 2014050370W WO 2014128421 A1 WO2014128421 A1 WO 2014128421A1
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WIPO (PCT)
Prior art keywords
layer
substrate according
vitreous material
diffusing
mgo
Prior art date
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PCT/FR2014/050370
Other languages
French (fr)
Inventor
Bérangère RAGUENET
Original Assignee
Saint-Gobain Glass France
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Filing date
Publication date
Priority claimed from FR1351619A external-priority patent/FR3002533A1/en
Application filed by Saint-Gobain Glass France filed Critical Saint-Gobain Glass France
Priority to EP14713170.0A priority Critical patent/EP2958867A1/en
Priority to KR1020157025701A priority patent/KR20150125967A/en
Priority to US14/770,190 priority patent/US10084144B2/en
Priority to JP2015558532A priority patent/JP6449788B2/en
Priority to RU2015140758A priority patent/RU2683454C2/en
Priority to CN201480010391.3A priority patent/CN105073666B/en
Publication of WO2014128421A1 publication Critical patent/WO2014128421A1/en

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
    • C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/02—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass
    • C03C17/04—Surface treatment of glass, not in the form of fibres or filaments, by coating with glass by fritting glass powder
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3417—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials all coatings being oxide coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/062—Glass compositions containing silica with less than 40% silica by weight
    • C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
    • C03C3/066—Glass compositions containing silica with less than 40% silica by weight containing boron containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/20—Compositions for glass with special properties for chemical resistant glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/85—Arrangements for extracting light from the devices
    • H10K50/854—Arrangements for extracting light from the devices comprising scattering means
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
    • C03C2217/45—Inorganic continuous phases
    • C03C2217/452—Glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/40—Coatings comprising at least one inhomogeneous layer
    • C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
    • C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
    • C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
    • C03C2217/475—Inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/77—Coatings having a rough surface
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2102/00—Constructional details relating to the organic devices covered by this subclass
    • H10K2102/10—Transparent electrodes, e.g. using graphene
    • H10K2102/101—Transparent electrodes, e.g. using graphene comprising transparent conductive oxides [TCO]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Definitions

  • the invention relates to the field of substrates for organic light - emitting diode devices. It relates more specifically to chemical compositions of vitreous material and glass frits particularly well suited to the formation of layers.
  • Organic light-emitting diode devices which will be referred to hereinafter by their acronym OLED, usually used in the art, are devices emitting light by means of a phenomenon of electroluminescence. These OLED devices generally include an organic electroluminescent system between two electrodes. One of the electrodes is deposited on a glass sheet in the form of an electroconductive layer. OLED devices can be used as display screens or as lighting devices.
  • the light extracted from the device is a white, polychromatic light.
  • the light extraction efficiency is, however, naturally low, of the order of 0.25, the light being trapped inside the device because of differences in refractive indices between its different elements.
  • vitreous materials whose chemical composition comprises 40 to 60% by weight of B1 2 O 3 and 5 to 30% by weight of ZnO.
  • the vitreous materials are generally obtained by a process in which a glass frit (with the same chemical composition as the material) is mixed with a typically organic medium to form a paste, which is deposited on the glass sheet before it is baked. .
  • the glass transition temperature of the glass frit must be low enough to be able to cook at temperatures at which the glass sheet can not be deformed. At the same time, the frit must not crystallize (devitrify) during cooking, which would have the effect of generating too much roughness and high optical absorption.
  • the linear thermal expansion coefficient of the frit must also be adapted to that of the glass sheet, generally be close to the latter, or slightly lower, in order to avoid during the cooling the appearance in the glassy material of mechanical stresses susceptible to damage it.
  • the object of the invention is to provide compositions of vitreous material (and glass frit) having a good compromise between improved chemical resistance, in particular to acids, a high refractive index, a coefficient of thermal expansion and a transition temperature. vitreous, and low ability to devitrification.
  • the subject of the invention is a diffusing substrate for an organic light-emitting diode device comprising a glass sheet coated on one of its faces with a layer comprising a vitreous material, such that said vitreous material has a chemical composition comprising the following constituents, varying within the weight limits defined below:
  • the invention also relates to an organic light-emitting diode device comprising a diffusing substrate according to the invention, wherein an electroconductive layer is disposed on the layer comprising a vitreous material.
  • an electroconductive layer is disposed on the layer comprising a vitreous material.
  • the subject of the invention is also a glass frit whose chemical composition comprises the following constituents, varying within the weight limits defined below:
  • the preferred characteristics in terms of oxide contents concern both the chemical composition of the vitreous material deposited on the glass sheet and that of the glass frit (used for the deposition).
  • the contents indicated are weight contents.
  • the weight content of Bi 2 0 3 is advantageously at least 62%, in particular 63% and even 64% or 65% and / or at most 83%, in particular 82% or even 81%, even 80%, 79%. % or 78%. It is preferably in a range from 65 to 80%, especially 68 to 75%.
  • a too low content of Bi 2 0 3 does not make it possible to obtain the desired refractive indices, while too high a content leads to unacceptable glass yellowing.
  • the weight content of B 2 O 3 is preferably at least 6%, especially 7% or 7.5% and / or at most 11%, especially 10%, or even 9.5% or 9%. It is preferably in a range from 6 to 11%, especially from 7 to 10%.
  • a high content of B 2 O 3 has the effect of increasing the glass transition temperature and lowering the chemical resistance of the material, while a too low content makes the glass more easily devitrifiable.
  • the weight content of SiO 2 is preferably at least 7%, especially 7.5% or even 8% and / or at most 18%, 17%, 16%, 15%, 14%, or 13% including 12% or 11% and even 10% or 9%. It is preferably in a range from 7 to 12%, especially 7.5 to 10%. An excessively high content of SiO 2 causes a detrimental reduction in the refractive index, while a too low content decreases both the chemical resistance and the thermal stability.
  • the weight content of ZnO is preferably at most 9.5%, especially 9% or 8%, even 7% or 6% or 5%, and even less than 5%. According to one embodiment, the ZnO content is even at most 1%, especially 0.5%, or 0.1%, or even zero.
  • the weight content of ZnO is preferably in a range from 2 to 8%, especially from 3 to 6%. High levels of ZnO are detrimental to good chemical resistance, particularly to acids, and increase the risk of devitrification.
  • the weight content of MgO is preferably at most 3%, especially 2.5% and even 2%. In some embodiments, this content is even less than 0.5% and even 0.1%, or even zero. In another embodiment, the MgO content is at least 0.5%, especially 1%, more particularly in a range from 0.5 to 3%, especially 1 to 2.5%. The addition of MgO makes it possible to improve the chemical resistance of the vitreous material.
  • the sum of the weight contents of MgO and ZnO is advantageously at least 1%, in particular 2% or 3% and even 4 or 5% and / or at most 9%, in particular 8% and even 7%. It is preferably in a range from 2 to 9%, especially 3 to 8% or 2 to 5%. It appeared that a cumulative content of MgO and ZnO too high resulted in a risk of devitrification during the manufacture of the frit.
  • the weight content of CaO is preferably at most 4% and even 3% or 2%. In some embodiments, this content is even less than 0.5% and even 0.1%, or even zero. In another embodiment, the CaO content is at least 0.5%, especially 1%, more particularly in a range of 1 to 4%, especially 1.5 to 3.5%.
  • the sum of the weight contents of CaO and MgO is preferably at least 0.5%, especially 1% or 1.5%, or even 2% or 3%. According to one embodiment, it may, however, be less than 0.5% and even 0.1%, or even zero.
  • the sum of the weight contents of CaO and MgO is preferably in a range from 0.5 to 4%.
  • the addition of CaO and / or MgO, in addition to a decrease in the ZnO content improves the acid resistance of the vitreous material.
  • the content of Al 2 O 3 is preferably at least 1%, especially 2%. It is preferably in a range from 1 to 6% or 1 to 4%, especially 2 to 3%.
  • the addition of alumina improves the chemical resistance of the material.
  • the BaO content is advantageously at most 10%, especially 5% and even 3% or even 1% or 0.5%, or even 0.1%. It can even be zero.
  • the total content of alkaline oxides (Li 2 0, Na 2 ⁇ 0, K 2 O) is preferably at most 3%, especially 2% and even 1% or 0.5%. According to a preferred embodiment, this content is preferably in a range from 0.02 to 1%, especially from 0.05 to 0.2%. In this case, the only alkaline oxide present is advantageously Na 2 ⁇ 0.
  • the addition of alkaline oxides, even at low levels, has the effect of significantly reducing the glass transition temperature.
  • each of the lower bounds can be combined with each of the upper bounds, the set of possible ranges not being recalled here for the sake of brevity.
  • each range for a given oxide can be combined with any other range for the other oxides.
  • not all combinations can be indicated so as not to unnecessarily burden the present text.
  • Tables 1 and 2 define 10 particularly preferred compositions resulting from combinations of ranges defined above. It goes without saying that each of these ranges can be combined with any other range from tables for other oxides.
  • the sum of the weight contents of Bi 2 O 3 , B 2 O 3 , SiO 2 , ZnO, MgO, BaO and CaO is at least 95%, especially 96% or 97% and even 98% or 99% .
  • the sum of the weight contents of B1 2 O 3 , B 2 O 3 , SiO 2 , ZnO, MgO and CaO is at least 95%, especially 96% or 97% and even 98% or 99%.
  • the total content of P 2 O 5 , b 2 0 5 and V 2 0 5 is preferably at most 1%, especially 0.5%, and even zero.
  • the composition is preferably free of lead oxide.
  • the chemical composition of the vitreous material or the frit may advantageously comprise the oxides T1O 2 and / or SnO 2 , which have proved to be particularly effective in terms of improving the resistance to acids.
  • the T1O 2 content is preferably at least 0.5% or 1% and / or at most 5% / 2% in particular.
  • the content of SnO 2 is preferably at least 0.2% or 0.5% and / or at most 5%, especially 3% or 2%.
  • the total content of T1O 2 and ZrO 2 is at most 1%, especially 0.5% and even 0.1%, or even zero, these oxides may have an adverse effect on the devitrification of this type of glasses.
  • the total content of coloring elements (Fe 2 O 3 , CuO, CoO, Cr 2 O 3 , MnO 2 , Se, Ag, Cu, Au, Nd 2 O 3 , Er 2 O 3 ) is also preferably zero (except impurities inevitable).
  • Antimony oxide (Sb 2 O 3) can be added to the composition in order to reduce the light absorption of the layer, in particular to make it less yellow. Its content is preferably at least 1, especially 2% and / or at most 5%, especially 4 or 3%.
  • the refractive index for a wavelength of 550 nm of the glass constituting the vitreous material or the glass frit is preferably in a range from 1.8 to 2.2, in particular from 1.85 to 2, 1, and even 1.88 to 2.0, or even 1.89 to 1.98.
  • the glass transition temperature Tg of the glass constituting the vitreous material or the glass frit is preferably in a range from 440 to 500 ° C., in particular from 450 to 480 ° C.
  • the glass transition temperature is measured by Differential Scanning Calorimetry (DSC), under nitrogen, with a temperature rise rate of 10 ° C / min. We consider here the beginning of the curve ("onset temperature") for the determination of the Tg.
  • the difference between the crystallization temperature Tx and the glass transition temperature Tg is preferably at least 100 ° C in order to avoid any devitrification of the vitreous material during its shaping.
  • the crystallization temperature is determined by taking into consideration the start of the crystallization (onset temperature) curve, obtained by differential scanning calorimetry.
  • the linear thermal expansion coefficient between 20 and 300 ° C of the glass constituting the vitreous material or the glass frit is preferably in a range from 70 to 100.10 -7 / ° C, particularly 75 to 95.10 "7 ° C, and even 80 to 90.10 " 7 ° C
  • the glass sheet preferably has a refractive index for a wavelength of 550 nm in a range from 1.4 to 1.6. It is preferably a glass of the silico-soda-lime type, obtained by the floating process (known as the "float" process), discharging the molten glass onto a molten tin bath.
  • the glass sheet is preferably colorless and has a light transmittance of at least 80% or even 90% within the meaning of EN 410: 1998.
  • the thickness of the glass sheet is preferably in a range from 0.1 to 6 mm, in particular from 0.3 to 3 mm.
  • the glass sheet is coated on one of its faces with a layer comprising a vitreous material.
  • this layer is deposited in contact with the glass sheet.
  • the layer covers at least 80%, especially 90% and even 95% of the surface of the glass sheet.
  • the layer is advantageously made of vitreous material.
  • the glass sheet diffuses the light (it may be in particular a satin glass, for example by an acid treatment), or that a layer diffuser is disposed under the layer comprising a vitreous material, in particular in contact with both the glass sheet and the layer consisting of vitreous material.
  • the diffusing aspect is thus not obtained by the layer itself.
  • the layer comprising a vitreous material further comprises diffusing elements.
  • the layer is even advantageously made of vitreous material and diffusing elements.
  • the layer is itself diffusing, and it will be called diffusing layer.
  • the diffusing elements are chosen from particles and cavities.
  • the diffusing layer can contain both particles and cavities.
  • the particles are preferably chosen from particles of alumina, zirconia, silica, titanium dioxide, calcium carbonate and barium sulfate.
  • the diffusing layer may comprise a single type of particles, or several different types of particles.
  • the cavities are preferably formed during cooking by removal of organic compounds, for example medium. They are preferably closed and not connected.
  • the diffusing elements preferably have a characteristic dimension allowing diffusion of the visible light, especially between 200 nm and 5 ⁇ m. A characteristic dimension may be a median diameter.
  • the mass concentration of particles in the diffusing layer is preferably in a range from 0.2 to 10%, especially from 0.5 to 8%, and even from 0.8 to 5%.
  • the diffusing elements can be distributed homogeneously in the vitreous material. They may alternatively be distributed in a heterogeneous manner, for example by providing gradients.
  • the diffusing layer may also consist of several elementary layers differentiating from each other by a different nature, size or proportion of diffusing elements.
  • the physical thickness of the layer comprising a vitreous material is preferably in a range from 0.5 to 100 ⁇ m, especially from 1 to 80 ⁇ m and more particularly from 2 to 60 ⁇ m, or even from 2 to 30 ⁇ m.
  • Other layers may be deposited on the layer comprising a vitreous material, and in particular in contact with it. It may for example be a planarization layer, intended to cover any particles located on the surface of the layer comprising a vitreous material, in particular of the diffusing layer, so as to reduce the roughness of the latter.
  • the planarization layer may for example consist of the vitreous material defined above, or of another vitreous material.
  • a barrier layer for example silica or silicon nitride, the thickness of which is in particular in a range from 5 to 30 nm, may be deposited on the layer comprising a glassy material or the planarization layer, in contact with it .
  • the blur is at least 40%, especially 50%, and even 60% or 70%, even 80%.
  • the blur sometimes called “sail” is measured by a haze-meter according to ASTM D1003.
  • the layer comprising a vitreous material is advantageously coated with an electroconductive layer.
  • the latter is preferably in direct contact with the layer comprising a vitreous material, or optionally with the planarization layer or the barrier layer.
  • the electroconductive layer is preferably based on a transparent conductive oxide (TCO), such as, for example, indium tin oxide (ITO).
  • TCO transparent conductive oxide
  • ITO indium tin oxide
  • Other conductive materials are possible, for example silver layers or conductive polymers.
  • the diffusing substrate may thus comprise (or consist of), by way of examples: A non-diffusing glass sheet, then a diffusing layer consisting of the vitreous material and diffusing elements, then (optionally) a planarization layer, then (optionally) a barrier layer, and finally an electroconductive layer, each layer mentioned being in direct contact with the layer which precedes it and the layer which follows it,
  • a non-diffusing glass sheet then a diffusing layer, then a layer made of vitreous material, then (optionally) a barrier layer, and finally an electroconductive layer, each layer mentioned being in direct contact with the layer that precedes it and the layer that follows it,
  • a diffusing glass sheet then a layer consisting of the glassy material, then (optionally) a barrier layer, and finally an electroconductive layer, each layer mentioned being in direct contact with the layer that precedes and the layer that follows.
  • the glass sheet coated with the layer comprising a vitreous material and the electroconductive layer (acting as a first electrode) is associated with an organic electroluminescent system in the form of a less a layer of organic material, itself coated with an electroconductive layer acting as second electrode.
  • the organic electroluminescent system is therefore located between the substrate and the second electrode, in direct contact with the first and the second electrode.
  • the electroluminescent system is preferably composed of several layers: hole injection layer (for example polyethylene dioxythiophene doped with polystyrene sulfonic acid or copper phthalocyanine), hole transport layer (for example triphenylamine derivatives), emission layer (for example metal complexes of quinoline derivatives), electron transport layer (for example, oxadiazole, triazole, bathophenanthroline derivatives, etc.), layer of injection of electrons (for example lithium or cesium) etc.
  • hole injection layer for example polyethylene dioxythiophene doped with polystyrene sulfonic acid or copper phthalocyanine
  • hole transport layer for example triphenylamine derivatives
  • emission layer for example metal complexes of quinoline derivatives
  • electron transport layer for example, oxadiazole, triazole, bathophenanthroline derivatives, etc.
  • layer of injection of electrons for example lithium or cesium
  • the OLED device according to the invention is preferably used as a source of polychromatic lighting, in particular white light. It is preferably a rear-emission device in the sense that light is emitted through the glass sheet.
  • the second electrode is made of a reflective material, for example a metal film, in particular aluminum, silver, magnesium, etc.
  • the OLED device therefore comprises successively a glass sheet, a layer comprising a vitreous material, optionally a barrier or planarization layer, an electroconductive layer (typically made of ITO), a multi-layer electroluminescent system and a reflecting electrode.
  • the glass frit according to the invention is preferably obtained by melting raw materials and then forming the frit.
  • the raw materials (oxides, carbonates, etc.) can be melted at temperatures of the order of 950 to 1100 ° C., and then the glass obtained can be cast, for example rolled between two rolls.
  • the glass obtained can then be milled, for example in a ball mill, a jet mill, a ball mill, or an attritor mill.
  • the glass frit is preferably in the form of particles whose dgo is at most 10 ⁇ m, in particular 5 ⁇ m, or even 4 ⁇ m.
  • the distribution of Particle diameters can be determined using a laser granulometer.
  • the layer comprising a vitreous material is preferably obtained by a process in which:
  • the glass frit according to the invention is mixed with an organic medium so as to form a paste
  • the organic medium is typically selected from alcohols, glycols, terpineol esters.
  • the mass proportion of medium is preferably in a range from 10 to 50%.
  • the deposition of the paste can be carried out in particular by screen printing, by roll coating, by dipping, by knife application, by spraying, by spinning, by vertical layering or by means of a slot-shaped die (slot die coating).
  • a screen made of textile or metal mesh, layering tools and a doctor blade the control of the thickness being ensured by the choice of the mesh of the screen and its tension, by the choice of the distance between the glass sheet and the screen, by the pressures and speeds of movement of the doctor blade.
  • the deposits are typically dried at a temperature of 100 to 150 ° C by infrared or ultraviolet radiation depending on the nature of the medium.
  • the firing is preferably carried out in an oven at a temperature in a range from 500 to 600 ° C, especially from 510 to 580 ° C.
  • the electroconductive layer may be deposited by a variety of thin film deposition techniques, such as for example the cathodic sputtering technique, in particular assisted by magnetic field (magnetron process), chemical vapor deposition (CVD), in particular assisted by plasma (PECVD, APPECVD), or liquid deposition.
  • Different glass frits were obtained by melting raw materials. To do this, sufficient raw materials were carried to obtain 300 g of glass for 1 h 30 at a temperature of 1000 ° C in crucibles heated by Joule effect of 400 cm 3 .
  • Tg glass transition temperature
  • T x crystallization temperature
  • n the refractive index for a wavelength of 550 nm
  • the leaching of bismuth in an acid medium denoted L and expressed in mg / l.
  • the T x is measured by differential scanning calorimetry.
  • Bismuth leaching was measured by dipping glass substrates coated with a layer of the glassy material studied in an acidic solution. To do this, layers 10 .mu.m thick were deposited by screen printing on soda-lime-calcium glass substrates, from frits having a d90 of 3.4 .mu.m and a d50 of 1.7 .mu.m.
  • the acid solution is a solution based on acetic acid sold under the Neutrax reference by the company Franklab, diluted to 1.3% by volume in deionized water to reach a pH of 3.
  • Comparative Examples C1 to C5 devitrify too easily to be shaped glassy material, hence their very high light absorption.
  • the examples according to the invention all have significantly better acid resistance than that of Comparative Example C6.
  • the resistance to the bases was also evaluated by measuring the mass loss (denoted "Mb") obtained after immersing the samples in a pH11 solution (solution diluted to 1% of the concentrate marketed by Borer under the trade name deconex® PV 110) for 18 h at 50 ° C.
  • Mb mass loss

Abstract

The invention relates to a diffusing substrate for a device having an organic light-emitting diode including a sheet of glass coated on one of the surfaces thereof with a layer including a vitreous material, such that said vitreous material has a chemical composition including the following components, which vary within the weight limits defined below: Bi2O3 60-85%, B2O3 5-12%, SiO2 6-20%, MgO+ZnO 0-9.5%, Al2O3 0-7%, Li2O+Na2O+K2O 0-5%, CaO 0-5%, BaO 0-20%.

Description

SUBSTRAT POUR DISPOSITIF A DIODE ELECTROLUMINESCENTE  SUBSTRATE FOR ELECTROLUMINESCENT DIODE DEVICE
ORGANIQUE  ORGANIC
L' invention se rapporte au domaine des substrats pour dispositifs à diode électroluminescente organique. Elle concerne plus précisément des compositions chimiques de matériau vitreux et de frittes de verre particulièrement bien adaptées à la formation de couches. Les dispositifs à diode électroluminescente organique, que nous appellerons dans la suite du texte selon leur acronyme anglais OLED, usuellement utilisé dans la technique, sont des dispositifs émettant de la lumière grâce à un phénomène d' électroluminescence . Ces dispositifs OLED comprennent généralement un système électroluminescent organique entre deux électrodes. Une des électrodes est déposée sur une feuille de verre sous la forme d'une couche électro-conductrice. Les dispositifs OLED peuvent être utilisés comme écrans de visualisation ou comme dispositifs d'éclairage. The invention relates to the field of substrates for organic light - emitting diode devices. It relates more specifically to chemical compositions of vitreous material and glass frits particularly well suited to the formation of layers. Organic light-emitting diode devices, which will be referred to hereinafter by their acronym OLED, usually used in the art, are devices emitting light by means of a phenomenon of electroluminescence. These OLED devices generally include an organic electroluminescent system between two electrodes. One of the electrodes is deposited on a glass sheet in the form of an electroconductive layer. OLED devices can be used as display screens or as lighting devices.
Dans une application en tant que dispositif d'éclairage (lampe etc.), la lumière extraite du dispositif est une lumière blanche, polychromatique . L'efficacité d'extraction de la lumière est toutefois naturellement faible, de l'ordre de 0,25, la lumière étant piégée à l'intérieur du dispositif du fait des différences d'indices de réfraction entre ses différents éléments. In an application as a lighting device (lamp, etc.), the light extracted from the device is a white, polychromatic light. The light extraction efficiency is, however, naturally low, of the order of 0.25, the light being trapped inside the device because of differences in refractive indices between its different elements.
Pour résoudre ce problème, il est connu, par exemple de la demande WO 2011/089343, de disposer entre la feuille de verre (d'indice 1,5 lorsqu'elle est en verre silico- sodo-calcique) et l'électrode, une couche diffusante interne comprenant un matériau vitreux d' indice de réfraction élevé (typiquement entre 1,7 et 2,0) et des éléments diffusants, par exemple des particules. La demande susmentionnée décrit des matériaux vitreux dont la composition chimique comprend 40 à 60% en poids de B12O3 et 5 à 30% en poids de ZnO. To solve this problem, it is known, for example from the application WO 2011/089343, to arrange between the glass sheet (of index 1.5 when it is made of soda-lime glass) and the electrode, an internal diffusing layer comprising a vitreous material of high refraction (typically between 1.7 and 2.0) and diffusing elements, for example particles. The aforementioned application describes vitreous materials whose chemical composition comprises 40 to 60% by weight of B1 2 O 3 and 5 to 30% by weight of ZnO.
Les matériaux vitreux sont généralement obtenus par un procédé dans lequel on mélange une fritte de verre (de même composition chimique que le matériau) et un médium typiquement organique pour former une pâte, que l'on dépose sur la feuille de verre avant de la cuire. The vitreous materials are generally obtained by a process in which a glass frit (with the same chemical composition as the material) is mixed with a typically organic medium to form a paste, which is deposited on the glass sheet before it is baked. .
La température de transition vitreuse de la fritte de verre doit être suffisamment basse afin de pouvoir cuire à des températures auxquelles la feuille de verre ne peut pas se déformer. En même temps, la fritte ne doit pas cristalliser (dévitrifier) lors de la cuisson, ce qui aurait pour effet de générer une rugosité trop importante ainsi qu'une absorption optique élevée. The glass transition temperature of the glass frit must be low enough to be able to cook at temperatures at which the glass sheet can not be deformed. At the same time, the frit must not crystallize (devitrify) during cooking, which would have the effect of generating too much roughness and high optical absorption.
Le coefficient de dilatation thermique linéaire de la fritte doit également être adapté à celui de la feuille de verre, généralement être proche de ce dernier, ou légèrement inférieur, afin d'éviter lors du refroidissement l'apparition dans le matériau vitreux de contraintes mécaniques susceptibles de l'endommager. The linear thermal expansion coefficient of the frit must also be adapted to that of the glass sheet, generally be close to the latter, or slightly lower, in order to avoid during the cooling the appearance in the glassy material of mechanical stresses susceptible to damage it.
Afin d'éviter le dépôt de poussières sur la couche susceptible de créer un court-circuit, il est d'usage de procéder à un nettoyage poussé de la couche avant le dépôt de la couche électro-conductrice. Ce nettoyage met généralement en œuvre des passages dans des cuves à ultrasons où la couche est soumise à l'action de détergents, successivement basiques (pour décoller les particules restées en surface) et acides (afin de neutraliser la surface de la couche et éviter tout redépôt de particules). L'attaque acide est susceptible de dégrader le matériau vitreux, créant une rugosité de surface inacceptable pour l'application finale. In order to prevent the deposit of dust on the layer likely to create a short circuit, it is customary to carry out a thorough cleaning of the layer before the deposition of the electroconductive layer. This cleaning usually involves passages in ultrasonic tanks where the layer is subjected to the action of detergents, successively basic (to take off particles remained on the surface) and acids (to neutralize the surface of the layer and avoid any redeposition of particles). Acid attack is likely to degrade the vitreous material, creating an unacceptable surface roughness for the final application.
L' invention a pour but de proposer des compositions de matériau vitreux (et de fritte de verre) présentant un bon compromis entre une résistance chimique améliorée, notamment aux acides, un indice de réfraction élevé, un coefficient de dilatation thermique et une température de transition vitreuse adaptés, et une faible aptitude à la dévitrification . A cet effet, l'invention a pour objet un substrat diffusant pour dispositif à diode électroluminescente organique comprenant une feuille de verre revêtue sur une de ses faces d'une couche comprenant un matériau vitreux, telle que ledit matériau vitreux possède une composition chimique comprenant les constituants suivants, variant dans les limites pondérales ci-après définies :  The object of the invention is to provide compositions of vitreous material (and glass frit) having a good compromise between improved chemical resistance, in particular to acids, a high refractive index, a coefficient of thermal expansion and a transition temperature. vitreous, and low ability to devitrification. To this end, the subject of the invention is a diffusing substrate for an organic light-emitting diode device comprising a glass sheet coated on one of its faces with a layer comprising a vitreous material, such that said vitreous material has a chemical composition comprising the following constituents, varying within the weight limits defined below:
Bi203 60-85% Bi 2 0 3 60-85%
B203 5-12% B 2 0 3 5-12%
Si02 6-20% Si0 2 6-20%
MgO+ZnO 0-9,5%  MgO + ZnO 0-9.5%
A1203 0-7%, notamment 0-5% A1 2 0 3 0-7%, especially 0-5%
Li20+Na20+K20 0-5% Li 2 0 + Na 2 0 + K 2 0 0-5%
CaO 0-5% CaO 0-5%
BaO 0-20%. L'invention a également pour objet un dispositif à diode électroluminescente organique comprenant un substrat diffusant selon l'invention, dans lequel une couche électro-conductrice est disposée sur la couche comprenant un matériau vitreux. Par l'emploi de termes « sur » ou « sous », on n'entend pas nécessairement que les couches soient en contact, seulement qu'elles soient plus proches du substrat (« sous ») ou plus éloignées (« sur ») . Le cas où les couches sont en contact n'est toutefois pas exclu. BaO 0-20%. The invention also relates to an organic light-emitting diode device comprising a diffusing substrate according to the invention, wherein an electroconductive layer is disposed on the layer comprising a vitreous material. By the use of "over" or "under" terms, one does not necessarily mean that the layers are in contact, only that they are closer to the substrate ("under") or more distant ("on"). The case where the layers are in contact is however not excluded.
L'invention a aussi pour objet une fritte de verre dont la composition chimique comprend les constituants suivants, variant dans les limites pondérales ci-après définies : The subject of the invention is also a glass frit whose chemical composition comprises the following constituents, varying within the weight limits defined below:
Bi203 65-85% Bi 2 0 3 65-85%
B203 5-12% B 2 0 3 5-12%
Si02 6-20% Si0 2 6-20%
MgO+ZnO 0-9, 5% MgO + ZnO 0-9, 5%
A1203 0-5% A1 2 0 3 0-5%
Li20+Na20+K20 0-5% Li 2 0 + Na 2 0 + K 2 0 0-5%
CaO 0-5% CaO 0-5%
CaO+MgO >0, 5 CaO + MgO> 0, 5
BaO 0-20%. BaO 0-20%.
Les caractéristiques préférées en termes de teneurs en oxydes qui sont détaillées ci-après concernent aussi bien la composition chimique du matériau vitreux déposé sur la feuille de verre que celle de la fritte de verre (utilisée pour le dépôt) . Dans l'ensemble du texte, les teneurs indiquées sont des teneurs pondérales. La teneur pondérale en Bi203 est avantageusement d' au moins 62%, notamment 63% et même 64% ou 65% et/ou d'au plus 83%, notamment 82%, voire 81%, même 80%, 79% ou 78%. Elle est de préférence comprise dans un domaine allant de 65 à 80%, notamment de 68 à 75%. Une teneur trop faible en Bi203 ne permet pas d'obtenir les indices de réfraction désirés, tandis qu'une teneur trop élevée conduit à un jaunissement du verre inacceptable. The preferred characteristics in terms of oxide contents which are detailed below concern both the chemical composition of the vitreous material deposited on the glass sheet and that of the glass frit (used for the deposition). Throughout the text, the contents indicated are weight contents. The weight content of Bi 2 0 3 is advantageously at least 62%, in particular 63% and even 64% or 65% and / or at most 83%, in particular 82% or even 81%, even 80%, 79%. % or 78%. It is preferably in a range from 65 to 80%, especially 68 to 75%. A too low content of Bi 2 0 3 does not make it possible to obtain the desired refractive indices, while too high a content leads to unacceptable glass yellowing.
La teneur pondérale en B2O3 est de préférence d' au moins 6%, notamment 7% ou 7,5% et/ou d'au plus 11%, notamment 10%, voire 9,5% ou 9%. Elle est de préférence comprise dans un domaine allant de 6 à 11%, notamment de 7 à 10%. Une teneur élevée en B2O3 a pour effet d'augmenter la température de transition vitreuse et d'abaisser la résistance chimique du matériau, tandis qu'une teneur trop faible rend le verre plus facilement dévitrifiable . The weight content of B 2 O 3 is preferably at least 6%, especially 7% or 7.5% and / or at most 11%, especially 10%, or even 9.5% or 9%. It is preferably in a range from 6 to 11%, especially from 7 to 10%. A high content of B 2 O 3 has the effect of increasing the glass transition temperature and lowering the chemical resistance of the material, while a too low content makes the glass more easily devitrifiable.
La teneur pondérale en S1O2 est de préférence d'au moins 7%, notamment 7,5% ou même 8% et/ou d'au plus 18%, 17%, 16%, 15%, 14%, ou 13%, notamment 12% ou 11% et même 10 % ou 9% . Elle est de préférence comprise dans un domaine allant de 7 à 12%, notamment de 7,5 à 10%. Une teneur trop forte en Si02 entraîne une baisse préjudiciable de l'indice de réfraction, tandis qu'une teneur trop faible diminue à la fois la résistance chimique et la stabilité thermique. The weight content of SiO 2 is preferably at least 7%, especially 7.5% or even 8% and / or at most 18%, 17%, 16%, 15%, 14%, or 13% including 12% or 11% and even 10% or 9%. It is preferably in a range from 7 to 12%, especially 7.5 to 10%. An excessively high content of SiO 2 causes a detrimental reduction in the refractive index, while a too low content decreases both the chemical resistance and the thermal stability.
La teneur pondérale en ZnO est de préférence d' au plus 9,5%, notamment 9% ou 8%, voire 7% ou encore 6% ou 5%, et même inférieure à 5%. Selon un mode de réalisation, la teneur en ZnO est même d'au plus 1%, notamment 0,5% , ou 0,1%, voire nulle. La teneur pondérale en ZnO est de préférence comprise dans un domaine allant de 2 à 8%, notamment de 3 à 6%. Des teneurs élevées en ZnO vont à 1' encontre d'une bonne résistance chimique, en particulier aux acides, et augmentent le risque de dévitrification. The weight content of ZnO is preferably at most 9.5%, especially 9% or 8%, even 7% or 6% or 5%, and even less than 5%. According to one embodiment, the ZnO content is even at most 1%, especially 0.5%, or 0.1%, or even zero. The weight content of ZnO is preferably in a range from 2 to 8%, especially from 3 to 6%. High levels of ZnO are detrimental to good chemical resistance, particularly to acids, and increase the risk of devitrification.
La teneur pondérale en MgO est de préférence d' au plus 3%, notamment 2,5% et même 2%. Dans certains mode de réalisation, cette teneur est même inférieure à 0,5% et même 0,1%, voire nulle. Dans un autre mode de réalisation, la teneur en MgO est d'au moins 0,5%, notamment 1%, plus particulièrement comprise dans un domaine allant de 0,5 à 3%, notamment de 1 à 2,5%. L'ajout de MgO permet d'améliorer la résistance chimique du matériau vitreux. The weight content of MgO is preferably at most 3%, especially 2.5% and even 2%. In some embodiments, this content is even less than 0.5% and even 0.1%, or even zero. In another embodiment, the MgO content is at least 0.5%, especially 1%, more particularly in a range from 0.5 to 3%, especially 1 to 2.5%. The addition of MgO makes it possible to improve the chemical resistance of the vitreous material.
La somme des teneurs pondérales en MgO et ZnO (MgO+ZnO) est avantageusement d'au moins 1%, notamment 2% ou 3% et même 4 ou 5% et/ou d'au plus 9%, notamment 8% et même 7%. Elle est de préférence comprise dans un domaine allant de 2 à 9%, notamment de 3 à 8% ou de 2 à 5% . Il est apparu qu'une teneur cumulée en MgO et ZnO trop élevée entraînait un risque de dévitrification lors de la fabrication de la fritte. The sum of the weight contents of MgO and ZnO (MgO + ZnO) is advantageously at least 1%, in particular 2% or 3% and even 4 or 5% and / or at most 9%, in particular 8% and even 7%. It is preferably in a range from 2 to 9%, especially 3 to 8% or 2 to 5%. It appeared that a cumulative content of MgO and ZnO too high resulted in a risk of devitrification during the manufacture of the frit.
La teneur pondérale en CaO est de préférence d' au plus 4% et même 3% ou 2%. Dans certains mode de réalisation, cette teneur est même inférieure à 0,5% et même 0,1%, voire nulle. Dans un autre mode de réalisation, la teneur en CaO est d'au moins 0,5%, notamment 1%, plus particulièrement comprise dans un domaine allant de 1 à 4%, notamment de 1,5 à 3,5%. The weight content of CaO is preferably at most 4% and even 3% or 2%. In some embodiments, this content is even less than 0.5% and even 0.1%, or even zero. In another embodiment, the CaO content is at least 0.5%, especially 1%, more particularly in a range of 1 to 4%, especially 1.5 to 3.5%.
La somme des teneurs pondérales en CaO et MgO est de préférence d'au moins 0,5%, notamment 1% ou 1,5%, voire 2% ou 3%. Selon un mode de réalisation elle peut toutefois être inférieure à 0,5% et même 0,1%, voire nulle. La somme des teneurs pondérales en CaO et MgO est de préférence comprise dans un domaine allant de 0,5 à 4%. L'ajout de CaO et/ou de MgO, en complément d'une baisse de la teneur en ZnO améliore la résistance aux acides du matériau vitreux. The sum of the weight contents of CaO and MgO is preferably at least 0.5%, especially 1% or 1.5%, or even 2% or 3%. According to one embodiment, it may, however, be less than 0.5% and even 0.1%, or even zero. The sum of the weight contents of CaO and MgO is preferably in a range from 0.5 to 4%. The addition of CaO and / or MgO, in addition to a decrease in the ZnO content improves the acid resistance of the vitreous material.
La teneur en AI2O3 est de préférence d'au moins 1%, notamment 2%. Elle est de préférence comprise dans un domaine allant de 1 à 6% ou de 1 à 4%, notamment de 2 à 3%. L'ajout d'alumine permet d'améliorer la résistance chimique du matériau. La teneur en BaO est avantageusement d'au plus 10%, notamment 5% et même 3% ou encore 1% ou 0,5%, voire 0,1%. Elle peut même être nulle. The content of Al 2 O 3 is preferably at least 1%, especially 2%. It is preferably in a range from 1 to 6% or 1 to 4%, especially 2 to 3%. The addition of alumina improves the chemical resistance of the material. The BaO content is advantageously at most 10%, especially 5% and even 3% or even 1% or 0.5%, or even 0.1%. It can even be zero.
La teneur totale en oxydes alcalins (Li20, Na2<0, K2O) est de préférence d'au plus 3%, notamment 2% et même 1% ou 0,5%. Selon un mode de réalisation préféré, cette teneur est de préférence comprise dans un domaine allant de 0,02 à 1%, notamment de 0,05 à 0,2%. Dans ce cas, le seul oxyde alcalin présent est avantageusement Na2<0. L'ajout d'oxydes alcalins, même à faible teneur, a pour effet de diminuer sensiblement la température de transition vitreuse. The total content of alkaline oxides (Li 2 0, Na 2 <0, K 2 O) is preferably at most 3%, especially 2% and even 1% or 0.5%. According to a preferred embodiment, this content is preferably in a range from 0.02 to 1%, especially from 0.05 to 0.2%. In this case, the only alkaline oxide present is advantageously Na 2 <0. The addition of alkaline oxides, even at low levels, has the effect of significantly reducing the glass transition temperature.
Pour chacun des oxydes ou groupes d'oxydes précités, chacune des bornes inférieures peut être combinée avec chacune des bornes supérieures, l'ensemble des plages possibles n'étant pas rappelé ici dans un souci de concision. De même, chaque plage pour un oxyde donné peut être combinée avec toute autre plage pour les autres oxydes. Ici encore, toutes les combinaisons ne peuvent être indiquées pour ne pas alourdir inutilement le présent texte. Certaines combinaisons préférées sont rappelées dans les tableaux 1 et 2 ci-après. For each of the oxides or groups of oxides mentioned above, each of the lower bounds can be combined with each of the upper bounds, the set of possible ranges not being recalled here for the sake of brevity. Similarly, each range for a given oxide can be combined with any other range for the other oxides. Here again, not all combinations can be indicated so as not to unnecessarily burden the present text. Some preferred combinations are recalled in Tables 1 and 2 below.
1 2 3 4 5 1 2 3 4 5
Bi203 60-85 65-80 70-78 65-80 65-80 Bi 2 0 3 60-85 65-80 70-78 65-80 65-80
B203 5-12 6-11 7-10 6-11 6-11 B 2 0 3 5-12 6-11 7-10 6-11 6-11
Si02 6-20 7-12 7,5-10 7-12 7-12 Si0 2 6-20 7-12 7.5-10 7-12 7-12
MgO+ZnO 0-9, 5 2-9 3-8 2-5 2-9 MgO + ZnO 0-9, 5 2-9 3-8 2-5 2-9
AI2O3 0-5 1-4 2-3 1-4 1-4 AI2O3 0-5 1-4 2-3 1-4 1-4
Li20+Na20+K20 0-5 0-2 0,05-0,2 0-2 0-2 Li 2 0 + Na 2 0 + K 2 0 0-5 0-2 0.05-0.2 0-2 0-2
CaO 0-5 0-3 0-2 0-3 1-4 CaO 0-5 0-3 0-2 0-3 1-4
BaO 0-20 0-5 0-1 0-5 0-5 BaO 0-20 0-5 0-1 0-5 0-5
Tableau 1 Table 1
Figure imgf000009_0001
Figure imgf000009_0001
Tableau 2 Les tableaux 1 et 2 définissent 10 compositions particulièrement préférées, issues de combinaisons de plages définies précédemment. Il va de soi que chacune de ces plages peut être combinée avec toute autre plage issue des tableaux pour les autres oxydes. Table 2 Tables 1 and 2 define 10 particularly preferred compositions resulting from combinations of ranges defined above. It goes without saying that each of these ranges can be combined with any other range from tables for other oxides.
De préférence, la somme des teneurs pondérales en Bi203, B203, Si02, ZnO, MgO, BaO et CaO est d'au moins 95%, notamment 96% ou 97% et même 98% ou 99%. De préférence, la somme des teneurs pondérales en B12O3, B2O3, Si02, ZnO, MgO et CaO est d'au moins 95%, notamment 96% ou 97% et même 98% ou 99%. Preferably, the sum of the weight contents of Bi 2 O 3 , B 2 O 3 , SiO 2 , ZnO, MgO, BaO and CaO is at least 95%, especially 96% or 97% and even 98% or 99% . Preferably, the sum of the weight contents of B1 2 O 3 , B 2 O 3 , SiO 2 , ZnO, MgO and CaO is at least 95%, especially 96% or 97% and even 98% or 99%.
La teneur totale en P2O5, b205 et V205 est de préférence d'au plus 1%, notamment 0,5%, et même nulle. La composition est de préférence dépourvue d'oxyde de plomb. The total content of P 2 O 5 , b 2 0 5 and V 2 0 5 is preferably at most 1%, especially 0.5%, and even zero. The composition is preferably free of lead oxide.
La composition chimique du matériau vitreux ou de la fritte peut avantageusement comprendre les oxydes T1O2 et/ou SnÛ2, qui se sont révélés particulièrement efficaces en termes d'amélioration de la résistance aux acides. La teneur en T1O2 est de préférence d'au moins 0,5% ou 1% et/ou d' au plus 5% / notamment 2%. La teneur en SnÛ2 est de préférence d'au moins 0,2% ou 0,5% et/ou d'au plus 5%, notamment 3% ou 2%. The chemical composition of the vitreous material or the frit may advantageously comprise the oxides T1O 2 and / or SnO 2 , which have proved to be particularly effective in terms of improving the resistance to acids. The T1O 2 content is preferably at least 0.5% or 1% and / or at most 5% / 2% in particular. The content of SnO 2 is preferably at least 0.2% or 0.5% and / or at most 5%, especially 3% or 2%.
Selon un autre mode de réalisation, la teneur totale en T1O2 et ZrÛ2 est d'au plus 1%, notamment 0,5% et même 0,1%, voire nulle, ces oxydes pouvant avoir un effet néfaste sur la dévitrification de ce type de verres. According to another embodiment, the total content of T1O 2 and ZrO 2 is at most 1%, especially 0.5% and even 0.1%, or even zero, these oxides may have an adverse effect on the devitrification of this type of glasses.
La teneur totale en éléments colorants (Fe2Û3, CuO, CoO, Cr203, Mn02, Se, Ag, Cu, Au, Nd203, Er203) est également de préférence nulle (sauf impuretés inévitables) . The total content of coloring elements (Fe 2 O 3 , CuO, CoO, Cr 2 O 3 , MnO 2 , Se, Ag, Cu, Au, Nd 2 O 3 , Er 2 O 3 ) is also preferably zero (except impurities inevitable).
De l'oxyde d'antimoine (Sb2Û3) peut être ajouté à la composition afin de réduire l'absorption lumineuse de la couche, en particulier de la rendre moins jaune. Sa teneur est de préférence d'au moins 1, notamment 2% et/ou d'au plus 5%, notamment 4 ou 3%. L'indice de réfraction pour une longueur d'onde de 550 nm du verre constituant le matériau vitreux ou la fritte de verre est de préférence compris dans un domaine allant de 1,8 à 2,2, notamment de 1,85 à 2,1, et même de 1,88 à 2,0, voire de 1,89 à 1,98. Antimony oxide (Sb 2 O 3) can be added to the composition in order to reduce the light absorption of the layer, in particular to make it less yellow. Its content is preferably at least 1, especially 2% and / or at most 5%, especially 4 or 3%. The refractive index for a wavelength of 550 nm of the glass constituting the vitreous material or the glass frit is preferably in a range from 1.8 to 2.2, in particular from 1.85 to 2, 1, and even 1.88 to 2.0, or even 1.89 to 1.98.
La température de transition vitreuse Tg du verre constituant le matériau vitreux ou la fritte de verre est de préférence comprise dans un domaine allant de 440 à 500°C, notamment de 450 à 480°C. La température de transition vitreuse est mesurée par calorimétrie différentielle à balayage (aussi appelée DSC - pour Differential Scanning Calorimetry) , sous azote, avec une vitesse de montée en température de 10°C/minute. On considère ici le début de la courbe (« onset température ») pour la détermination de la Tg. The glass transition temperature Tg of the glass constituting the vitreous material or the glass frit is preferably in a range from 440 to 500 ° C., in particular from 450 to 480 ° C. The glass transition temperature is measured by Differential Scanning Calorimetry (DSC), under nitrogen, with a temperature rise rate of 10 ° C / min. We consider here the beginning of the curve ("onset temperature") for the determination of the Tg.
La différence entre la température de cristallisation Tx et la température de transition vitreuse Tg est de préférence d'au moins 100°C afin d'éviter toute dévitrification du matériau vitreux durant sa mise en forme. La température de cristallisation est déterminée en prenant en considération le début de la courbe (« onset température ») de cristallisation, obtenue par calorimétrie différentielle à balayage. The difference between the crystallization temperature Tx and the glass transition temperature Tg is preferably at least 100 ° C in order to avoid any devitrification of the vitreous material during its shaping. The crystallization temperature is determined by taking into consideration the start of the crystallization (onset temperature) curve, obtained by differential scanning calorimetry.
Le coefficient de dilatation thermique linéaire entre 20 et 300°C du verre constituant le matériau vitreux ou la fritte de verre est de préférence compris dans un domaine allant de 70 à 100.10~7/°C, notamment 75 à 95.10"7°C, et même 80 à 90.10"7°C The linear thermal expansion coefficient between 20 and 300 ° C of the glass constituting the vitreous material or the glass frit is preferably in a range from 70 to 100.10 -7 / ° C, particularly 75 to 95.10 "7 ° C, and even 80 to 90.10 " 7 ° C
La feuille de verre présente de préférence un indice de réfraction pour une longueur d'onde de 550 nm comprise dans un domaine allant de 1,4 à 1,6. Il s'agit de préférence d'un verre du type silico-sodo-calcique, obtenu par le procédé de flottage (dit procédé « float ») , consistant à déverser le verre fondu sur un bain d' étain en fusion. La feuille de verre est de préférence incolore, et présente un facteur de transmission lumineuse d'au moins 80%, voire 90% au sens de la norme EN 410 :1998. L'épaisseur de la feuille de verre est de préférence comprise dans un domaine allant de 0,1 à 6 mm, notamment de 0 , 3 à 3 mm . The glass sheet preferably has a refractive index for a wavelength of 550 nm in a range from 1.4 to 1.6. It is preferably a glass of the silico-soda-lime type, obtained by the floating process (known as the "float" process), discharging the molten glass onto a molten tin bath. The glass sheet is preferably colorless and has a light transmittance of at least 80% or even 90% within the meaning of EN 410: 1998. The thickness of the glass sheet is preferably in a range from 0.1 to 6 mm, in particular from 0.3 to 3 mm.
La feuille de verre est revêtue sur une de ses faces d'une couche comprenant un matériau vitreux. De préférence, cette couche est déposée en contact avec la feuille de verre. Avantageusement, la couche revêt au moins 80%, notamment 90% et même 95% de la surface de la feuille de verre . The glass sheet is coated on one of its faces with a layer comprising a vitreous material. Preferably, this layer is deposited in contact with the glass sheet. Advantageously, the layer covers at least 80%, especially 90% and even 95% of the surface of the glass sheet.
Selon un mode de réalisation de l'invention, la couche est avantageusement constituée du matériau vitreux. Dans ce cas, et afin d'obtenir un substrat diffusant, il est préférable que la feuille de verre diffuse la lumière (il peut s'agir notamment d'un verre satiné, par exemple par un traitement acide), ou qu'une couche diffusante soit disposée sous la couche comprenant un matériau vitreux, notamment en contact avec à la fois la feuille de verre et la couche constituée du matériau vitreux. L'aspect diffusant n'est donc pas obtenu par la couche elle-même.  According to one embodiment of the invention, the layer is advantageously made of vitreous material. In this case, and in order to obtain a diffusing substrate, it is preferable that the glass sheet diffuses the light (it may be in particular a satin glass, for example by an acid treatment), or that a layer diffuser is disposed under the layer comprising a vitreous material, in particular in contact with both the glass sheet and the layer consisting of vitreous material. The diffusing aspect is thus not obtained by the layer itself.
Selon un autre mode de réalisation de l'invention, la couche comprenant un matériau vitreux comprend en outre des éléments diffusants. La couche est même avantageusement constituée du matériau vitreux et des éléments diffusants. Dans ce mode de réalisation, la couche est elle-même diffusante, et on la qualifiera de couche diffusante. De préférence, les éléments diffusants sont choisis parmi les particules et les cavités. La couche diffusante peut contenir à la fois des particules et des cavités. Les particules sont de préférence choisies parmi les particules d'alumine, de zircone, de silice, de dioxyde de titane, de carbonate de calcium, de sulfate de baryum. La couche diffusante peut comprendre un seul type de particules, ou plusieurs types de particules différentes. According to another embodiment of the invention, the layer comprising a vitreous material further comprises diffusing elements. The layer is even advantageously made of vitreous material and diffusing elements. In this embodiment, the layer is itself diffusing, and it will be called diffusing layer. Preferably, the diffusing elements are chosen from particles and cavities. The diffusing layer can contain both particles and cavities. The particles are preferably chosen from particles of alumina, zirconia, silica, titanium dioxide, calcium carbonate and barium sulfate. The diffusing layer may comprise a single type of particles, or several different types of particles.
Les cavités sont de préférence formées lors de la cuisson par élimination de composés organiques, par exemple du médium. Elles sont de préférence fermées et non connectées . Les éléments diffusants présentent de préférence une dimension caractéristique permettant une diffusion de la lumière visible, notamment comprise entre 200 nm et 5 ym. Une dimension caractéristique peut être un diamètre médian. The cavities are preferably formed during cooking by removal of organic compounds, for example medium. They are preferably closed and not connected. The diffusing elements preferably have a characteristic dimension allowing diffusion of the visible light, especially between 200 nm and 5 μm. A characteristic dimension may be a median diameter.
La concentration massique de particules dans la couche diffusante est de préférence comprise dans un domaine allant de 0,2 à 10%, notamment de 0,5 à 8%, et même de 0,8 à 5%. The mass concentration of particles in the diffusing layer is preferably in a range from 0.2 to 10%, especially from 0.5 to 8%, and even from 0.8 to 5%.
Les éléments diffusants peuvent être répartis de manière homogène dans le matériau vitreux. Ils peuvent alternativement être répartis de manière hétérogène, en ménageant par exemple des gradients. La couche diffusante peut également être constituée de plusieurs couches élémentaires se différenciant l'une de l'autre par une nature, une taille ou une proportion différente d'éléments diffusants. The diffusing elements can be distributed homogeneously in the vitreous material. They may alternatively be distributed in a heterogeneous manner, for example by providing gradients. The diffusing layer may also consist of several elementary layers differentiating from each other by a different nature, size or proportion of diffusing elements.
L'épaisseur physique de la couche comprenant un matériau vitreux est de préférence comprise dans un domaine allant de 0,5 à 100 ym, notamment de 1 à 80 ym et plus particulièrement de 2 à 60 ym, voire de 2 à 30 ym. D' autres couches peuvent être déposées sur la couche comprenant un matériau vitreux, et notamment en contact avec elle. Il peut par exemple s'agir d'une couche de planarisation, destinée à recouvrir d'éventuelles particules situées en surface de la couche comprenant un matériau vitreux, notamment de la couche diffusante, de manière à réduire la rugosité de cette dernière. La couche de planarisation peut par exemple être constituée du matériau vitreux défini précédemment, ou d'un autre matériau vitreux. The physical thickness of the layer comprising a vitreous material is preferably in a range from 0.5 to 100 μm, especially from 1 to 80 μm and more particularly from 2 to 60 μm, or even from 2 to 30 μm. Other layers may be deposited on the layer comprising a vitreous material, and in particular in contact with it. It may for example be a planarization layer, intended to cover any particles located on the surface of the layer comprising a vitreous material, in particular of the diffusing layer, so as to reduce the roughness of the latter. The planarization layer may for example consist of the vitreous material defined above, or of another vitreous material.
Une couche barrière, par exemple en silice ou nitrure de silicium, dont l'épaisseur est notamment comprise dans un domaine allant de 5 à 30 nm, peut être déposée sur la couche comprenant un matériau vitreux ou la couche de planarisation, en contact avec elle. A barrier layer, for example silica or silicon nitride, the thickness of which is in particular in a range from 5 to 30 nm, may be deposited on the layer comprising a glassy material or the planarization layer, in contact with it .
Par l'emploi de l'adjectif « diffusant » pour qualifier le substrat et le cas échéant la feuille de verre ou la couche comprenant un matériau vitreux, on entend de préférence que le flou est d'au moins 40%, notamment 50%, et même 60% ou 70%, voire 80%. Le flou, parfois appelé « voile » est mesuré par un haze-meter selon la norme ASTM D1003. By the use of the adjective "diffusing" to describe the substrate and, where appropriate, the glass sheet or the layer comprising a vitreous material, it is preferably understood that the blur is at least 40%, especially 50%, and even 60% or 70%, even 80%. The blur, sometimes called "sail" is measured by a haze-meter according to ASTM D1003.
La couche comprenant un matériau vitreux est avantageusement revêtue d'une couche électro-conductrice. Cette dernière est de préférence en contact direct avec la couche comprenant un matériau vitreux, ou le cas échéant avec la couche de planarisation ou la couche barrière. La couche électro-conductrice est de préférence à base d'un oxyde conducteur transparent (TCO) , tel que par exemple l'oxyde d' indium et d' étain (ITO). D'autres matériaux conducteurs sont possibles, par exemple des couches d'argent ou encore des polymères conducteurs. The layer comprising a vitreous material is advantageously coated with an electroconductive layer. The latter is preferably in direct contact with the layer comprising a vitreous material, or optionally with the planarization layer or the barrier layer. The electroconductive layer is preferably based on a transparent conductive oxide (TCO), such as, for example, indium tin oxide (ITO). Other conductive materials are possible, for example silver layers or conductive polymers.
Le substrat diffusant peut ainsi comprendre (ou être constituée de), à titre d'exemples : Une feuille de verre non-diffusante, puis une couche diffusante constituée du matériau vitreux et d'éléments diffusants, puis (optionnellement ) une couche de planarisation, puis (optionnellement) une couche barrière, et enfin une couche électro-conductrice, chaque couche citée étant en contact direct avec la couche qui la précède et la couche qui la suit, The diffusing substrate may thus comprise (or consist of), by way of examples: A non-diffusing glass sheet, then a diffusing layer consisting of the vitreous material and diffusing elements, then (optionally) a planarization layer, then (optionally) a barrier layer, and finally an electroconductive layer, each layer mentioned being in direct contact with the layer which precedes it and the layer which follows it,
Une feuille de verre non-diffusante, puis une couche diffusante, puis une couche constituée du matériau vitreux, puis (optionnellement) une couche barrière, et enfin une couche électro-conductrice, chaque couche citée étant en contact direct avec la couche qui la précède et la couche qui la suit, A non-diffusing glass sheet, then a diffusing layer, then a layer made of vitreous material, then (optionally) a barrier layer, and finally an electroconductive layer, each layer mentioned being in direct contact with the layer that precedes it and the layer that follows it,
Une feuille de verre diffusante, puis une couche constituée du matériau vitreux, puis (optionnellement) une couche barrière, et enfin une couche électro-conductrice, chaque couche citée étant en contact direct avec la couche qui la précède et la couche qui la suit. A diffusing glass sheet, then a layer consisting of the glassy material, then (optionally) a barrier layer, and finally an electroconductive layer, each layer mentioned being in direct contact with the layer that precedes and the layer that follows.
Dans le dispositif à diode électroluminescente organique selon l'invention, la feuille de verre revêtue de la couche comprenant un matériau vitreux et de la couche électro-conductrice (faisant office de première électrode) est associée à un système électroluminescent organique sous forme d'au moins une couche de matériau organique, lui-même revêtu d'une couche électro-conductrice faisant office de seconde électrode. Le système électroluminescent organique est donc situé entre le substrat et la seconde électrode, en contact direct avec la première et la seconde électrode. In the organic light-emitting diode device according to the invention, the glass sheet coated with the layer comprising a vitreous material and the electroconductive layer (acting as a first electrode) is associated with an organic electroluminescent system in the form of a less a layer of organic material, itself coated with an electroconductive layer acting as second electrode. The organic electroluminescent system is therefore located between the substrate and the second electrode, in direct contact with the first and the second electrode.
Le système électroluminescent est de préférence composé de plusieurs couches : couche d'injection de trous (par exemple en polyéthylène dioxythiophene dopé avec de l'acide polystyrène sulfonique ou en phtalocyanine de cuivre) , couche de transport de trous (par exemple en dérivés de triphénylamine) , couche d'émission (par exemple en complexes métalliques de dérivés de la quinoline) , couche de transport d'électrons (par exemple en dérivés d' oxadiazole, de triazole, de bathophenanthroline...) , couche d'injection d'électrons (par exemple en lithium ou césium) etc.. The electroluminescent system is preferably composed of several layers: hole injection layer (for example polyethylene dioxythiophene doped with polystyrene sulfonic acid or copper phthalocyanine), hole transport layer (for example triphenylamine derivatives), emission layer (for example metal complexes of quinoline derivatives), electron transport layer (for example, oxadiazole, triazole, bathophenanthroline derivatives, etc.), layer of injection of electrons (for example lithium or cesium) etc.
Le dispositif OLED selon l'invention est de préférence employé comme source d'éclairage polychromatique, notamment de lumière blanche. Il est de préférence un dispositif à émission par l'arrière, au sens où la lumière est émise à travers la feuille de verre. Dans ce cas, la seconde électrode est constituée d'un matériau réfléchissant, par exemple un film métallique, notamment d'aluminium, d'argent, de magnésium etc.. De préférence, le dispositif OLED comprend donc successivement une feuille de verre, une couche comprenant un matériau vitreux, éventuellement une couche barrière ou de planarisation, une couche électro-conductrice (typiquement en ITO) , un système électroluminescent composé de plusieurs couches et une électrode réfléchissante. The OLED device according to the invention is preferably used as a source of polychromatic lighting, in particular white light. It is preferably a rear-emission device in the sense that light is emitted through the glass sheet. In this case, the second electrode is made of a reflective material, for example a metal film, in particular aluminum, silver, magnesium, etc. Preferably, the OLED device therefore comprises successively a glass sheet, a layer comprising a vitreous material, optionally a barrier or planarization layer, an electroconductive layer (typically made of ITO), a multi-layer electroluminescent system and a reflecting electrode.
La fritte de verre selon l'invention est de préférence obtenue par fusion de matières premières puis mise en forme de fritte. Les matières premières (oxydes, carbonates...) peuvent être fondues à des températures de l'ordre de 950 à 1100°C, puis le verre obtenu peut être coulé, par exemple laminé entre deux rouleaux. Le verre obtenu peut ensuite être broyé, par exemple dans un broyeur à boulets, un broyeur à jet, un broyeur à billes, ou un broyeur par attrition. La fritte de verre se présente de préférence sous forme de particules dont le dgo est d'au plus 10 ym, notamment 5 ym, voire même 4 ym. La distribution de diamètres de particules peut être déterminée à l'aide d'un granulomètre laser. The glass frit according to the invention is preferably obtained by melting raw materials and then forming the frit. The raw materials (oxides, carbonates, etc.) can be melted at temperatures of the order of 950 to 1100 ° C., and then the glass obtained can be cast, for example rolled between two rolls. The glass obtained can then be milled, for example in a ball mill, a jet mill, a ball mill, or an attritor mill. The glass frit is preferably in the form of particles whose dgo is at most 10 μm, in particular 5 μm, or even 4 μm. The distribution of Particle diameters can be determined using a laser granulometer.
La couche comprenant un matériau vitreux est de préférence obtenue par un procédé dans lequel : The layer comprising a vitreous material is preferably obtained by a process in which:
- on mélange la fritte de verre selon l'invention à un médium organique de manière à former une pâte,  the glass frit according to the invention is mixed with an organic medium so as to form a paste,
- on dépose ladite pâte sur la feuille de verre, said paste is deposited on the glass sheet,
- on cuit l'ensemble. - we cook the whole.
Le médium organique est typiquement choisi parmi des alcools, des glycols, des esters de terpinéol. La proportion massique de médium est de préférence comprise dans un domaine allant de 10 à 50%. The organic medium is typically selected from alcohols, glycols, terpineol esters. The mass proportion of medium is preferably in a range from 10 to 50%.
Le dépôt de la pâte peut être réalisé notamment par sérigraphie, par dépôt au rouleau, par trempage, par application au couteau, par pulvérisation, par tournette, par nappage vertical ou encore à l'aide d'une filière en forme de fente (slot die coating) . The deposition of the paste can be carried out in particular by screen printing, by roll coating, by dipping, by knife application, by spraying, by spinning, by vertical layering or by means of a slot-shaped die (slot die coating).
Dans le cas de la sérigraphie, on utilise de préférence un écran en maille textile ou métallique, des outils de nappage et un racle, la maîtrise de l'épaisseur étant assurée par le choix de la maille de l'écran et sa tension, par le choix de la distance entre la feuille de verre et l'écran, par les pressions et vitesses de déplacement de la racle. Les dépôts sont typiquement séchés à une température de 100 à 150 °C par rayonnement infrarouge ou ultraviolet selon la nature du médium. In the case of screen printing, it is preferable to use a screen made of textile or metal mesh, layering tools and a doctor blade, the control of the thickness being ensured by the choice of the mesh of the screen and its tension, by the choice of the distance between the glass sheet and the screen, by the pressures and speeds of movement of the doctor blade. The deposits are typically dried at a temperature of 100 to 150 ° C by infrared or ultraviolet radiation depending on the nature of the medium.
La cuisson est de préférence réalisée dans un four à une température comprise dans un domaine allant de 500 à 600°C, notamment de 510 à 580°C. La couche électro-conductrice peut être déposée par diverses technique de dépôt de couches minces, telles que par exemple les technique de pulvérisation cathodique, notamment assistée par champ magnétique (procédé magnétron) , de dépôt chimique en phase vapeur (CVD) , notamment assistée par plasma (PECVD, APPECVD) , ou encore de dépôt par voie liquide. The firing is preferably carried out in an oven at a temperature in a range from 500 to 600 ° C, especially from 510 to 580 ° C. The electroconductive layer may be deposited by a variety of thin film deposition techniques, such as for example the cathodic sputtering technique, in particular assisted by magnetic field (magnetron process), chemical vapor deposition (CVD), in particular assisted by plasma (PECVD, APPECVD), or liquid deposition.
Les exemples qui suivent illustrent l'invention de manière non-limitative. The following examples illustrate the invention in a non-limiting manner.
Première série d'exemples First series of examples
Différentes frittes de verre ont été obtenues par fusion de matières premières. Pour ce faire, on a porté les matières premières suffisantes pour obtenir 300 g de verre pendant lh30 à une température de 1000°C dans des creusets chauffés par effet Joule de 400 cm3. Different glass frits were obtained by melting raw materials. To do this, sufficient raw materials were carried to obtain 300 g of glass for 1 h 30 at a temperature of 1000 ° C in crucibles heated by Joule effect of 400 cm 3 .
Les tableaux 3, 4 et 5 récapitulent les résultats obtenus. Dans ces tableaux sont indiqués : Tables 3, 4 and 5 summarize the results obtained. In these tables are indicated:
- la composition chimique de la fritte (en pourcentage pondéral d'oxyde), - the chemical composition of the frit (in weight percentage of oxide),
- la température de transition vitreuse, notée « Tg » et exprimée en °C, - la température de cristallisation, notée Tx et exprimée en °C. - The glass transition temperature, denoted "Tg" and expressed in ° C, - the crystallization temperature, denoted T x and expressed in ° C.
- le coefficient de dilatation thermique linéaire, noté a et exprimé en 10~7/K, the coefficient of linear thermal expansion, denoted a and expressed in 10 ~ 7 / K,
- l'indice de réfraction pour une longueur d'onde de 550 nm, noté n, mesuré par ellipsométrie, the refractive index for a wavelength of 550 nm, denoted n, measured by ellipsometry,
- l'absorption lumineuse pour une épaisseur de 3 mm, notée AL, mesurée par spectrophotométrie,the light absorption for a thickness of 3 mm, denoted AL, measured by spectrophotometry,
- la lixiviation du bismuth en milieu acide, notée L et exprimée en mg/L. Comme la Tg, la Tx est mesurée par calorimétrie différentielle à balayage. the leaching of bismuth in an acid medium, denoted L and expressed in mg / l. Like the Tg, the T x is measured by differential scanning calorimetry.
La lixiviation du bismuth a été mesurée en plongeant des substrats de verre revêtus d'une couche du matériau vitreux étudié dans une solution acide. Pour ce faire, des couches de 10 ym d'épaisseur ont été déposées par sérigraphie sur des substrats de verre silico-sodo- calcique, à partir de frittes ayant un d90 de 3,4 ym et un d50 de 1,7 ym. La solution acide est une solution à base d'acide acétique commercialisée sous la référence Neutrax par la société Franklab, diluée à 1,3% en volume dans de l'eau déionisée afin d'atteindre un pH de 3. Les échantillons ont été immergés dans cette solution à une température de 50 °C pendant une heure, et une petite quantité de solution a été prélevée toutes les 10 minutes puis analysée afin d'en déduire la quantité de B12O3 passé en solution. Le chiffre indiqué dans les tableaux correspond à la concentration en B12O3 dans la solution d'attaque après 10 minutes. Les exemples 1 à 10 (tableaux 3 et 4) sont des exemples selon l'invention, tandis que les exemples Cl à C6 sont des exemples comparatifs. Bismuth leaching was measured by dipping glass substrates coated with a layer of the glassy material studied in an acidic solution. To do this, layers 10 .mu.m thick were deposited by screen printing on soda-lime-calcium glass substrates, from frits having a d90 of 3.4 .mu.m and a d50 of 1.7 .mu.m. The acid solution is a solution based on acetic acid sold under the Neutrax reference by the company Franklab, diluted to 1.3% by volume in deionized water to reach a pH of 3. The samples were immersed in this solution at a temperature of 50 ° C for one hour, and a small amount of solution was taken every 10 minutes and analyzed to deduce the amount of B1 2 O 3 spent in solution. The figure in the tables corresponds to the concentration of B1 2 O 3 in the attack solution after 10 minutes. Examples 1 to 10 (Tables 3 and 4) are examples according to the invention, while Examples C1 to C6 are comparative examples.
1 2 3 4 51 2 3 4 5
Bi203 73, 1 74,5 73,7 72, 3 72,4Bi 2 0 3 73, 74.5 73.7 72, 3 72.4
ZnO 5, 54 5,31 5,39 9, 34 7, 9ZnO 5, 54 5.31 5.39 9, 34 7, 9
Si02 7, 9 7,7 7, 9 7, 6 9, 4Si0 2 7, 9 7.7 7, 9 7, 6 9, 4
B203 7,71 7,8 7,74 6, 31 6,86B 2 0 3 7.71 7.8 7.74 6, 31 6.86
AI2O3 2,5 2,5 2,4 2,4 2,5AI2O3 2.5 2.5 2.4 2.4 2.5
Na20 0,1 0,11 0,11 0,1 0,08Na 2 0 0.1 0.11 0.11 0.1 0.08
CaO 3,1 0 1,7 1, 9 0,04CaO 3.1 0 1.7 1, 9 0.04
MgO 0 2 1 0 0 MgO 0 2 1 0 0
MgO+ZnO 5, 54 7,31 6,39 9, 34 7, 9MgO + ZnO 5, 54 7.31 6.39 9, 34 7, 9
MgO+CaO 3,1 2 2,7 1, 9 0,04 MgO + CaO 3.1 2 2.7 1, 9 0.04
Tg(°C) 460 468 464 456 455Tg (° C) 460 468 464 456 455
Tx (°C) 693 678 668 a (10"7/K) 88,7 82, 2 84,2 84, 9 77,5 n 1, 91 1, 93 1, 93 1, 92 1, 90T x (° C) 693 678 668 a (10 "7 / K) 88.7 82, 84.2 84, 9 77.5 n 1, 91 1, 93 1, 93 1, 92 1, 90
AL (%) 9, 4 7,3 10,3 11, 1 7,4AL (%) 9, 4 7.3 10.3 11, 7.4
L (mg/L) 1, 6 1,5 1,56 1, 62 1,72 L (mg / L) 1, 6 1.5 1.56 1, 62 1.72
Tableau 3  Table 3
6 7 8 9 106 7 8 9 10
Bi2o3 72 74,8 75, 9 77,2 77Bi 2 o 3 72 74.8 75, 9 77.2 77
ZnO 4,87 2, 68 0,08 4,51 2,51ZnO 4.87 2, 68 0.08 4.51 2.51
Si02 11,4 9,2 8,4 7,8 7, 6Si0 2 11.4 9.2 8 7.4 7.8 7, 6
B203 8, 37 8,36 10,4 6, 18 9,46B 2 0 3 8, 37 8.36 10.4 6, 18 9.46
AI2O3 2,7 2,7 2, 6 2,3 2,4AI2O3 2.7 2.7 2, 6 2.3 2.4
Na20 0,09 0,08 0,09 0,09 0,09Na 2 0 0.09 0.08 0.09 0.09 0.09
CaO 0 0 0 0 0CaO 0 0 0 0 0
MgO 0 2,1 2,1 1, 9 1 MgO 0 2.1 2.1 1, 9 1
MgO+ZnO 4,87 4,78 2,18 6,41 3,51MgO + ZnO 4.87 4.78 2.18 6.41 3.51
MgO+CaO 0 2,1 2,1 1, 9 1 MgO + CaO 0 2.1 2.1 1, 9 1
Tg(°C) 457 475 478 475 458Tg (° C) 457 475 478 475 458
Tx (°C) 682 678 683 677 668 a (10"7/K) 76, 9 77, 1 86, 4 77,2 82, 9T x (° C) 682 678 683 677 668 a (10 -7 / K) 76, 9 77, 1 86, 777, 82, 9
AL (%) 8,3 10,5 8,5 7,3 8,1 n 1,89 1, 91 1,89 1, 96 1, 92AL (%) 8.3 10.5 8.5 7.3 8.1 n 1.89 1, 91 1.89 1, 96 1, 92
L (mg/L) 1,48 1, 52 1,42 1,76 1,7 L (mg / L) 1.48 1, 52 1.42 1.76 1.7
Tab] Leau 4 Cl C2 C3 C4 C5 C6 Tab] Water 4 C2 C2 C3 C4 C5 C6
Bi203 71, 9 72,7 72, 5 72,2 72, 3 70 Bi 2 O 3 71, 9 72.7 72, 72.2 72, 37
ZnO 10,7 10,7 10,4 9, 87 9, 23 10  ZnO 10.7 10.7 10.4 9, 87 9, 23 10
Si02 7,8 7, 6 7, 6 7, 6 7,8 7 Si0 2 7.8 7, 6 7, 6 7, 6 7.8 7
B203 5, 62 5,7 5, 8 6, 58 6,29 9 B 2 0 3 5, 62 5.7 5, 8 6, 58 6.29 9
AI2O3 2,5 2,4 2,4 2,5 2, 6 3  AI2O3 2.5 2.4 2.4 2.5 2, 6 3
Na20 0,1 0,09 0,11 0,1 0,1 1 Na 2 0 0.1 0.09 0.11 0.1 0.1 1
CaO 1,4 0 0,7 0 1 0  CaO 1.4 0 0.7 0 1 0
MgO 0 0, 9 0,4 1,2 0, 6 0  MgO 0 0, 9 0.4 1.2 0, 6 0
MgO+ZnO 10,7 11, 6 10,8 11, 07 9, 83 10 MgO + ZnO 10.7 11, 6 10.8 11, 07 9, 83 10
MgO+CaO 1,4 0, 9 1,1 1,2 1, 6 0  MgO + CaO 1.4 0, 9 1.1 1,2 1, 6 0
AL (%) 24,5 28, 6 22,4 22, 9 15, 8 -AL (%) 24.5 28, 6 22.4 22, 9 15, 8 -
L (mg/L) - - - - - 1, 9 L (mg / L) - - - - - 1, 9
Tableau 5  Table 5
Les exemples comparatifs Cl à C5 dévitrifient trop facilement pour pouvoir être mis en forme de matériau vitreux, d'où leur absorption lumineuse très élevée. Les exemples selon l'invention présentent tous une résistance aux acides significativement meilleure que celle de l'exemple comparatif C6. Comparative Examples C1 to C5 devitrify too easily to be shaped glassy material, hence their very high light absorption. The examples according to the invention all have significantly better acid resistance than that of Comparative Example C6.
Deuxième série d'exemples Second series of examples
D'autres verres selon l'invention ont été obtenus par fusion, comme dans le cas de la première série d'exemples. Leur composition chimique est indiquée au tableau 6 ci-après. Other glasses according to the invention were obtained by melting, as in the case of the first series of examples. Their chemical composition is shown in Table 6 below.
La résistance aux acides de ces verres a été évaluée sur les échantillons de verre massifs. Les échantillons, tous de même surface, ont été immergés dans la même solution d'attaque que celle décrite précédemment pendant une durée de 18 heures. La perte de masse de l'échantillon, exprimée en mg/cm2 est appelée « Ma » dans le tableau 6. La perte de masse dans le cas du verre comparatif C6 est de 15 mg/cm2. The acid resistance of these glasses was evaluated on the bulk glass samples. The samples, all of the same surface, were immersed in the same etching solution as previously described for a period of 18 hours. Mass loss of the sample, expressed in mg / cm 2 is called "Ma" in Table 6. The mass loss in the case of the comparative glass C6 is 15 mg / cm 2 .
La résistance aux bases a également été évaluée en mesurant la perte de masse (notée « Mb ») obtenue après avoir immergé les échantillons dans une solution à pHll (solution diluée à 1% du concentré commercialisé par la société Borer sous la marque deconex® PV 110) pendant 18 h à 50°C. The resistance to the bases was also evaluated by measuring the mass loss (denoted "Mb") obtained after immersing the samples in a pH11 solution (solution diluted to 1% of the concentrate marketed by Borer under the trade name deconex® PV 110) for 18 h at 50 ° C.
Figure imgf000022_0001
Figure imgf000022_0001
Tableau 6  Table 6

Claims

REVENDICATIONS
1. Substrat diffusant pour dispositif à diode électroluminescente organique comprenant une feuille de verre revêtue sur une de ses faces d'une couche comprenant un matériau vitreux, telle que ledit matériau vitreux possède une composition chimique comprenant les constituants suivants, variant dans les limites pondérales ci-après définies : 1. Diffusing substrate for an organic light-emitting diode device comprising a sheet of glass coated on one of its faces with a layer comprising a vitreous material, such that said vitreous material has a chemical composition comprising the following constituents, varying within the weight limits herein -after defined:
Bi203 60-85% Bi 2 0 3 60-85%
B203 5-12% B 2 0 3 5-12%
Si02 6-20% If0 2 6-20%
MgO+ZnO 0-9,5% A1203 0-7, notamment 0-5%% MgO+ZnO 0-9.5% A1 2 0 3 0-7, notably 0-5%%
Li20+Na20+K20 0-5% Li 2 0+Na 2 0+K 2 0 0-5%
CaO 0-5% CaO 0-5%
BaO 0-20%. BaO 0-20%.
2. Substrat diffusant selon la revendication précédente, tel que la teneur pondérale en Bi203 est comprise dans un domaine allant de 65 à 80%, notamment de 68 à 75%. 2. Diffusing substrate according to the preceding claim, such that the weight content of Bi 2 0 3 is included in a range ranging from 65 to 80%, in particular from 68 to 75%.
3. Substrat diffusant selon l'une des revendications précédentes, tel que la teneur pondérale en ZnO est d'au plus 8%, notamment est inférieure a 5%. 3. Diffusing substrate according to one of the preceding claims, such that the weight content of ZnO is at most 8%, in particular is less than 5%.
4. Substrat diffusant selon l'une des revendications précédentes, tel que la teneur pondérale en Si02 est comprise dans un domaine allant de 7 à 12%. 4. Diffusing substrate according to one of the preceding claims, such that the weight content of Si0 2 is included in a range ranging from 7 to 12%.
5. Substrat diffusant selon l'une des revendications précédentes, tel que la somme des teneurs pondérales en MgO et ZnO est comprise dans un domaine allant de 2 à 9%. 5. Diffusing substrate according to one of the preceding claims, such that the sum of the weight contents of MgO and ZnO is included in a range ranging from 2 to 9%.
6. Substrat diffusant selon l'une des revendications précédentes, tel que la somme des teneurs pondérales en CaO et MgO est comprise dans un domaine allant de 0,5 à 4%. 6. Diffusing substrate according to one of the preceding claims, such that the sum of the weight contents of CaO and MgO is included in a range ranging from 0.5 to 4%.
7. Substrat diffusant selon l'une des revendications précédentes, tel que la composition chimique du matériau vitreux comprend les oxydes T 1O2 et/ou Sn02 -7. Diffusing substrate according to one of the preceding claims, such that the chemical composition of the vitreous material comprises the oxides T 1O2 and/or Sn02 -
8. Substrat diffusant selon la revendication précédente, tel que la teneur en T 1O2 est d'au moins 0,5% ou 1% et d'au plus 5%, notamment 2%. 8. Diffusing substrate according to the preceding claim, such that the T 1O 2 content is at least 0.5% or 1% and at most 5%, in particular 2%.
9. Substrat diffusant selon la revendication 7 ou 8, tel que la teneur en Sn02 est d'au moins 0,2% ou 0,5% et d'au plus 5%, notamment 3% ou 2%. 9. Diffusing substrate according to claim 7 or 8, such that the Sn0 2 content is at least 0.2% or 0.5% and at most 5%, in particular 3% or 2%.
10. Substrat diffusant selon l'une des revendications précédentes, tel que la couche comprenant un matériau vitreux comprend en outre des éléments diffusants choisis parmi les particules et les cavités. 10. Diffusing substrate according to one of the preceding claims, such that the layer comprising a vitreous material further comprises diffusing elements chosen from particles and cavities.
11. Substrat selon la revendication précédente, tel que les particules sont choisies parmi les particules d'alumine, de zircone, de silice, de dioxyde de titane, de carbonate de calcium, de sulfate de baryum. 11. Substrate according to the preceding claim, such that the particles are chosen from particles of alumina, zirconia, silica, titanium dioxide, calcium carbonate, barium sulfate.
12. Substrat selon l'une des revendications 1 à 9, tel que la couche comprenant un matériau vitreux est constituée dudit matériau vitreux, et tel que la feuille de verre diffuse la lumière ou qu'une couche diffusante est disposée sous la couche comprenant un matériau vitreux. 12. Substrate according to one of claims 1 to 9, such that the layer comprising a vitreous material is made up of said vitreous material, and such that the glass sheet diffuses the light or that a diffusing layer is placed under the layer comprising a vitreous material.
13. Substrat diffusant selon l'une des revendications précédentes, tel qu'une couche électro-conductrice est disposée sur la couche comprenant un matériau vitreux . 13. Diffusing substrate according to one of the preceding claims, such that an electroconductive layer is placed on the layer comprising a vitreous material.
14. Dispositif à diode électroluminescente organique comprenant un substrat diffusant selon la revendication précédente . 14. Organic light-emitting diode device comprising a diffusing substrate according to the preceding claim.
15. Fritte de verre dont la composition chimique comprend les constituants suivants, variant dans les limites pondérales ci-après définies : 15. Glass frit whose chemical composition includes the following constituents, varying within the weight limits defined below:
Bi203 65-85% Bi 2 0 3 65-85%
B203 5-12% B 2 0 3 5-12%
Si02 6-20% If0 2 6-20%
MgO+ZnO 0-9, 5% MgO+ZnO 0-9.5%
A1203 0-5% A1 2 0 3 0-5%
Li20+Na20+K20 0-5% Li 2 0+Na 2 0+K 2 0 0-5%
CaO 0-5% CaO 0-5%
CaO+MgO >0, 5 CaO+MgO >0.5
BaO 0-20%. BaO 0-20%.
PCT/FR2014/050370 2013-02-25 2014-02-24 Substrate for device having an organic light-emitting diode WO2014128421A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10319934B2 (en) 2014-04-22 2019-06-11 Saint-Gobain Glass France Transparent supported electrode for OLED

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2983224B1 (en) * 2013-09-30 2020-08-26 LG Display Co., Ltd. Organic electronic device
ES2637715T3 (en) * 2014-12-01 2017-10-16 Saint-Gobain Glass France OLED substrate transparent diffuser and method to produce said substrate
US20170254930A1 (en) * 2016-03-03 2017-09-07 Corning Incorporated Structured light-transmitting articles and methods for making the same
WO2018071076A2 (en) * 2016-07-07 2018-04-19 Northwestern University Enhanced conductivity, adhesion and environmental stability of printed graphene inks with nitrocellulose
JP2019020723A (en) 2017-07-12 2019-02-07 Ｈｏｙａ Ｃａｎｄｅｏ Ｏｐｔｒｏｎｉｃｓ株式会社 Light guide plate and image display device
KR102642282B1 (en) * 2017-07-12 2024-02-28 호야 가부시키가이샤 Light guide plate and image display device

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070224429A1 (en) * 2006-03-23 2007-09-27 Keiichiro Hayakawa Dielectric and display device having a dielectric and dielectric manufacturing method
US20080185962A1 (en) * 2007-02-06 2008-08-07 Noritake Co., Limited Lead-free acid-resistant glass composition and glass paste comprised of the same
US20090004597A1 (en) * 2006-01-12 2009-01-01 Takenori Ueoka Photosensitive Composition, Display Member, and Process for Producing The Same
US20090042715A1 (en) * 2005-12-27 2009-02-12 Ichiro Uchiyama Lead-Free Bismuth Glass
WO2011089343A1 (en) 2010-01-22 2011-07-28 Saint-Gobain Glass France Glass substrate coated with a high-index layer under an electrode coating, and organic light-emitting device comprising such a substrate
US20120025245A1 (en) * 2009-01-26 2012-02-02 Asahi Glass Company, Limited Substrate for electronic device and electronic device using same
WO2012017183A1 (en) * 2010-08-06 2012-02-09 Saint-Gobain Glass France Support having a scattering layer for an organic light-emitting diode device, organic light-emitting device comprising such a support
WO2012035565A1 (en) * 2010-09-16 2012-03-22 Daunia Solar Cell S.R.L. Sealing agent with low softening temperature useful in the preparation of electronic devices

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6255239B1 (en) * 1998-12-04 2001-07-03 Cerdec Corporation Lead-free alkali metal-free glass compositions
WO2003087001A1 (en) * 2002-03-29 2003-10-23 Matsushita Electric Industrial Co., Ltd. Bismuth glass composition, and magnetic head and plasma display panel including the same as sealing member
US7494607B2 (en) * 2005-04-14 2009-02-24 E.I. Du Pont De Nemours And Company Electroconductive thick film composition(s), electrode(s), and semiconductor device(s) formed therefrom
WO2009014029A1 (en) * 2007-07-20 2009-01-29 Nippon Electric Glass Co., Ltd. Sealing material, sealing tablet, and glass composition for sealing
JP5309629B2 (en) 2008-03-13 2013-10-09 セントラル硝子株式会社 Lead-free glass composition having acid resistance
WO2010084922A1 (en) * 2009-01-26 2010-07-29 旭硝子株式会社 Glass for scattering layer of organic led device and organic led device
JP5768717B2 (en) * 2009-10-15 2015-08-26 旭硝子株式会社 Glass for scattering layer of organic LED element and organic LED element using the same
CN101891390B (en) * 2009-12-31 2012-09-05 四川虹欧显示器件有限公司 Lead-free medium slurry and manufacturing method thereof
US9224983B2 (en) * 2010-12-20 2015-12-29 Samsung Electronics Co., Ltd. Substrate for surface light emitting device and method of manufacturing the substrate, surface light emitting device, lighting apparatus, and backlight including the same

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090042715A1 (en) * 2005-12-27 2009-02-12 Ichiro Uchiyama Lead-Free Bismuth Glass
US20090004597A1 (en) * 2006-01-12 2009-01-01 Takenori Ueoka Photosensitive Composition, Display Member, and Process for Producing The Same
US20070224429A1 (en) * 2006-03-23 2007-09-27 Keiichiro Hayakawa Dielectric and display device having a dielectric and dielectric manufacturing method
US20080185962A1 (en) * 2007-02-06 2008-08-07 Noritake Co., Limited Lead-free acid-resistant glass composition and glass paste comprised of the same
US20120025245A1 (en) * 2009-01-26 2012-02-02 Asahi Glass Company, Limited Substrate for electronic device and electronic device using same
WO2011089343A1 (en) 2010-01-22 2011-07-28 Saint-Gobain Glass France Glass substrate coated with a high-index layer under an electrode coating, and organic light-emitting device comprising such a substrate
US20120313134A1 (en) * 2010-01-22 2012-12-13 Saint-Gobain Glass France Glass substrate coated with a high-index layer under an electrode coating, and organic light-emitting device comprising such a substrate
WO2012017183A1 (en) * 2010-08-06 2012-02-09 Saint-Gobain Glass France Support having a scattering layer for an organic light-emitting diode device, organic light-emitting device comprising such a support
WO2012035565A1 (en) * 2010-09-16 2012-03-22 Daunia Solar Cell S.R.L. Sealing agent with low softening temperature useful in the preparation of electronic devices

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10319934B2 (en) 2014-04-22 2019-06-11 Saint-Gobain Glass France Transparent supported electrode for OLED

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